Sulfolanyl sulfones



Patented Nov. 2, 1948 SULFOLANYL SULFONES ,flltupert 0. Morris, Berkeley, and Edward C.

Shokal, Gakland, Califi, assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware i No Drawing. Application (Dctober 22, 1945,

vSerial No. 623,865

.1 0 Claims. (01. 260-229) This invention relates to a novel and particularly useful class of =organic..-compounds having at least two vsulfonyl radicals, one of which is :a member of ;a cyclic sulfone group While the other is'directly attached to :a saturated carbon atom of said 2 radical. Thesecompounds may be represented by the general structuralformula R .1 R-* J o--R cyclic :'Sl11fO1l6lg1Qllp :and'is also directly linked to it it *aea-rbonatom.oianotherradical. The invention is also concerned with an lefficientrand economical method vfor the production of the new sulfones.

I The saturated cyclic sulfone radical of four saturated carbon atomsand a sulfur atom in a fiveamembered heterocyclic ring. having two oxygen atoms attached to the .sulfuratom, which is one characteristic of the novel compounds of the invention, has at various times in the past 1; been referred to was the thiolane-l,'1-dioxide radical,rthe cyclotetr-amethylene sulione radical, the .dihydrobultadiene sulione radical, and the fis-uliolanyl radical. The latter expression, deriuedlirom thename isul-folane given the simplest where at leas-tone of the R radicals is a sulfone radical, i. e. a hydrocarbon sulfonyl or a substituted hydrocarbon ,sulfonyl radical, while the other R radicals attached to the nuclear carbon atoms consisting of hydrogen and halogen atoms and hydroiiy, amino, sulfon'ic and organic radicals, preferably "hydrogen and hydrocarbon radicals such as ellkyl, a'lkenyl, cycloalkyl, cycloalkenyl, ary'l, *aralkyl or alkaryl radicals.

'Due to the unique structure, the suliolanyl sulare the :same or different members o'flthe group compound of this type which has the structural iormula cal. tially omprise a sulfolanyl radical having a hydrocarbon sulfonyl or a substituted hydrocarbon sulfonyl radical directly at'tached to at least one of .the nuclear carbon atoms of the .sulfolanyl Z P produced or suggested. They are stable comm 331 poundathe lower members' being solubleinwater,

" alcohol and like pol-arsol-vents, the solubility decreasingwith molecular weight so that those havwill be used herein as the most convenient and readily understandable term to generically define this arrangement of carbon atoms and a sulfonyl radical.

The compounds of theinvention are further characterized by thefact that one-of the saturated carbon atoms of the sulfolanyl radical is directly In other words, the new compounds essentones of the invention have properties "which make them unexpectedly superior to the sulfones of different structure which have been previously ing hydrocarbon chains of tenor more carbon atoms are substantially insoluble in such solvents but are soluble in hydrocarbons. The compounds of the invention have in general a preferential solubility for aromatic and unsaturated aliphatic or cycloaliphatic hydrocarb ons compared with the corresponding more saturated hydrocarbons which makes them highly useful in the separation attached to-a sulfone radical, that is, to sulfonyl of such compounds by extractive di till ti or liquid-liquid solvent extraction methods.

- 0 "The sulfolanyl sulfones miscible with natural or g synthetic resins, :plastics or'ru'bbers are of excepy 41) {tional value as plasticizers therefor, particularly in the preparation of clear, water-white products radical) which is also directly linked to-a carbon since the sulfolanyl sulfones of the invention are ato preferably, but not necessarily, a Saturated not subject to oxidation or discoloration, particu-' carbon atom of a monovalent hydrocarbon radilarly yellowing,-which are disadvantages associatcal, or substituted monovaflent yd oca r ed with the use of unsaturatedplasticizers. For

example, the alkyl and naphthenyl sulfolanyl sulfones having five to eight carbon atoms. in the alkyl .or n-aphthenyl group are particularly desirable plasticizers for cellulose acetate and vinyl chloridepolymers,

sulfolanyl sulfides.

As pointed out in copending application, .Serial No. 474,032, filed January 26, 1943, now Patent 2,393,925 of January 29, 1946 of which the present application is a continuation-in-part, the new sulfolanyl sulfones are remarkably effective insecticides, particularly against household pests such as flies. In this use they show an unexpected synergistic effect with other insecticides such as the ether thiocyan-ates and pyrethrum. In combination with these agents, the compounds of the invention produce a higher knock-down and kill according to modified Poet-Grady tests than is possible with either component alone in the same concentration. These properties of the novel suliolanyl sulfones could not have been foreseen and they make these compounds especially advantageous in their many applications.

An especially preferred subgroup of the novel compounds are the unsubstituted sulfolanyl sultones in which at least one hydrocarbon sulfonyl radical is directly attached to a nuclear carbon atom of a sulfolanyl radical, while the other free bonds of the nuclear carbon atoms of the sulfonyl radical are directly attached to hydrogen atoms'or monovalent hydrocarbon radicals. Compounds of this type in which .a single hydrocarbon sulfonyl radical, preferably an alkane 'sulfonyl radical of not more than 20 carbon atoms, is attached to the heterocyclic ring are especially advantageous. A novel subgroup of compounds of this type are the alkyl-3-sulfolanyl sulfones of the structural formula wherein the Rs (regardless of subscripts) are members of the group consisting of the hydrogen atom and the aliphatic hydrocarbon radicals. For example, when alkyl represents an amyl radical and all the Rs (regardless of subscripts) are each a hydrogen atom, the above formula represents amyl 3-suliolanyl sulfone, while when alkyl is'an amyl radical, R1 is a methyl radical and R; an ethyl radical the formula represents a-myl 2- rnethyll-ethyl-B-sulfolanyl sulfone.

For certain purposes, compounds of the above ,formula'in which R1 or R4 or Rs, preferably R4, is a hydrocarbon sulfonyl radical, for example, dimethyl 3,4-su1folanyl disulfone, 3-isopropyl 5-tbutyl 3,5-suliolanyl disulfone, and the like, are especially advantageous.

' A number of different methods are available for the production of new sulfolanyl sulfones of the invention. One which is of special advantage because of its efficiency and economy comprises oxidation of the corresponding sulfolanyl sulfides, which maybe readily prepared by addition of mercaptans to sulfolenes. The sulfolenes are compounds having the same structure as the previously described sulfolanes except that two adjoining carbon atoms of the heterocyclic ring are linkedby. an olefinicdouble bond instead of a single bond. Mercaptans of all kinds add readily to the double bond of the sulfolenes and form The reaction, which is preferably carriedout in the presence of a basic agent, is usually quite exothermic and it is generally advisable to control the conditions so that excessive temperature rises are avoided. While this may be achieved by cooling, it is preferred, in the interest of economy, to maintain the desired temperature by regulating the rate of addition of the reactants. For example, the sulfolene may be iii) 4 slowly added to the mercaptan, or vice versa, so as to keep the temperature within the preferred range of about 50 C. to C. The mercaptan generally adds according to Markownikofis rule but there is a tendency for the sulfide group to attach itself to the unsaturated carbon atom farthest removed from the sulfonyl radical. Thus, the same sulfide is formed by reacting tertiary butyl mercaptan with both 2-sulfolene and 3 sulfolene. Abnormal addition may be effected by carrying out the reaction'in the presence of peroxides or other sources of free radicals,for example, lead tetraethyl, etc.

As oxidizing agents for the conversion of sulfolanyl sulfides to sulfolanyl sulfones, potassium permanganate, hydrogen peroxide, sodium perchlorite, nitric acid and the like may be used. With saturated sulfides it is usually advantageous to use a stoichiometric excess of such oxidizing agents as more complete reaction may thereby be achieved in a reasonable time and purification of the sulfolanyl sulfone obtained is simplified. Especially where highly purified products are not required, it may be preferable to use about the stoichiometric requirement, or substantially small amounts, of oxidizing agent. This is also true where the starting sulfolanyl sulfide contains unsaturated" groups or substituents sue-- ceptible to oxidationwhich it is desired to preserve unchanged in the final sulfolanyl sulfone. In other cases the oxidation of such groups or substituents may not b'eundesirable and under such circumstances their conversion may be carried out simultaneously with the oxidation of the sulfide sulfur atom or atoms by using an appropriately larger amount of oxidizing agent. The oxidation may be carried out in the presence of an aqueous or other suitable solvent for the sulfolanyl sulfide being treated and/or the oxidizing agent it being generally advantageous to add the oxidizing agent to the sulfolanyl sulfide rather than vice versa inorder to reduce the possibility of excessive oxidation leading to undesirable side reactions, and to facilitate control of the temperature which should preferably be kept below about C. Oxidation with air or oxygen in the presence of suitable catalysts may also be used. i

The process may be carried out with pure or substantially pure individual sulfolanyl sulfides or with mixtures thereof. Particularly suitable sources of such mixtures are the sulfides formed by reacting one or more sulfolenes with the -rnixtures of mercaptans which are recovered in the refining of cracked gasoline or other petroleum products, or the mixtures of secondary mercaptans formed by adding hydrogen sulfide to cracked parafiin wax or fractions thereof. Another advantageous source of I mixed sulfides which are useful starting materials for the compounds of the invention is the reaction of sulfolenes with mercaptans formed by reaction of hydrogen sulfide with olefin polymers such, for example, as propylene or butylene polymers or copolymers. The sulfolanyl sulfides oxidized according to the invention need not be in a pure form but may be mixedlwith byproducts of the method of their formation, diluents or other compounds which do not interfere with the desired reaction.

An alternative method of producing the sulfo lanyl suliones, when the corresponding sulfolanyl sulfides are not readily available economically, comprises reacting suitable'halosulfolanes, preferably chloro, bromo or iodosulfones with alkyl,

eryi, alkaryl, aralkyl, or cycloaliphaticsulfinic acid salts. following equation for the production of ethyl The reaction: oes according to the 3-sulfolanyl sulfonefrom S-iodosulfolane and the potassium salt of ethyl sulfinic acid:

Boiling equal molecular amounts of the reactants in the presenceoi anaqueous or alcoholic medium at atmospheric pressure for about 20 minutes to an hour is usually an advantageous method of producing the new compounds of the invention according 'to this method. Chlorides react more slowly than the iodidesbut are generally much .cheaperto prepare. By this. method, for example, isopropyl2-sulfolanyl sulione is obtained from Z-iodosulfolane and sodium Z-propanesulfinate, and isoamyl 34-dimethyl-2-sulfolanyl sul- .fone is obtained from .2-chloro-3/i--dirnethylsulfolane andfpotassiuin B-methyl-l-butanesulfinate. 4-chloro-3-sulfolanol and ZA-dimethyl- 3,. l dichlorosulfolane are also suitable starting materials for the production of sulfolanyl sulfones according to this method. The method is 'o fspecial advantage for the production of sul- ,folanyl sulfones having .pclymerizable groups in the molecule since thereaction can be successiully carried out in the presence of polymerization inhibitors such as hydroquinone, p-t-butylcatechol, etc. and the desired monomeric unsaturated sulfolanyl sulfcnes recovered. For instance, allyl 2-iodo-4-sulfolanyl carbonatemay be converted to the corresponding methyl sulfone .b y reaction in the foregoing manner with the potassium salt of methanesulfinic acid and the pb-tained methyl(allyl-4-carbonate) -2-sulfolanyl sulion e polymerized to a hard, clear resin by warming with benzoyl peroxide.

1 Salts of sulfolanyl sulfinic acids, such as the potassium salt of 3-sulfolansulfinic acid, may be reacted in: the same way with halides suchas the butyl and cyclohexyl iodides or allyl iodide, etc, to produce the sulfolanyl sulfones of the invention. These sulfinic acids are new compounds which ,are the invention of the presentinventors, which may be obtained, for example, by oxidation of the corresponding dry sodium mercaptides in the air at moderately elevated temperatures. Thus, 3-sulfolanyl thiol producedby reacting 3-sulfolene with hydrogen sulfide may .be converted to the sodium mercaptide, oxidized ..bon atom or carbon atoms of the sulfolanyl radiamyl mercaptans (boiling point, 113 CAlltwi C.) equal to 7.59 moles, and 10 grams of sodium hydroxide was added "I08 grams (6.0 moles) of 3-sulfolene. The reaction was rather slow at room temperature; however, on warming to 45 0., an exothermic reaction took place and the kettle temperature rapidly rose. to 96 C. At the end of two hours at 50? (IL-65 (1a titration indicated that the experiment was 95.8% complete. At the end of 6 hours the reaction mix.- ture was washed a number oftimes with alkali and distilled. The product had a light yellow color and a strong odor of organic sulfide.

After a number of attempts it was found that 1 this objectionable odor could-be removed by treating the product with copper dust and Filter-Gel (manufactured by Filtrol Corporation, Los Angeles). The treatmentwas easily carried out by refluxing for an hour in an alcoholsolution or by heating on the steam bath. The result.- ing product had a mild, not unpleasant odor. A yield of 92.2% of thioether was obtained, based on the B-sulfolene used. This amyl B-suliolanyl sulfide is oxidized at room temperature with a stoichiornetric excess of potassium permanganate to amyl 3-sulfolanyl sulfone. An 86.6 weight per cent yieldis obtained of asolidprocluct which on crystallization from alcohol meltsat 1025C. Analysis of the product, which is substantially insoluble in petroleum ether and easily soluble in benzene, showed 25.2% sulfur compared with the calculated value of 25.19%. f

Example II Tertiary butyl mercaptan was slowly added to a rapidly stirred mixture of Z-sulfolene and sodium hydroxide. There was a rapid rise in temperature and at the end of approximately two hours the reaction was substantially complete. The resulting tertiary butyl 3-sulfolanyl sulfide (M. P. 72.3-72.8) is oxidized with an excess of potassium permanganate under the conditions of Example I and an excellent yield of t-butyl 3,"Sl .11 folanyl sulfone is obtained. On evaporation} of "an alcohol solution, this sulfone crystallizes as a White solid. l i

Using 3-sulfolene instead of 2 sulfolene. as th'e starting material, the same product is obtained.

Example III t A quantity of methallyl mercaptan was reacted with 3-sulfolene by the same method as.

was used in the preceding examples. A very vigorous exothermic reaction took place causing the loss of a part of the reaction mixture.

The recovered product, which distilled at 168 C.-180 C. under 2.5 mm. of mercury, is oxidized by hydrogen peroxide to methallyl 3-sulf0lanyl sulfone with some formation of viscous tarry material presumably resulting from polymerization.

Example IV In a flask was placed 296 g. (2.02 moles) of 2,4-

dimethyl-3-sulfoleneand 13 g. (0.20 mole) of ing amyl 2,4-dimethyl-3-su1folanyl sulfones are obtained in a good yield. The product purified by crystallization is a white solid substantially insoluble in aliphatic hydrocarbons.

Emample V A mixture of 0.394 mole of 2-methyl-3-sulfolene, 5.46 moles of amyl mercaptan and 2.5 g. of potassium hydroxide was heated at 60 C. for 48 hours to obtain amyl 2-methyl-3-sulfolanyl sulfide boiling at 157.8 C.-158.4 C. at less than -1 mm. Oxidation of this sulfide under the conditions used in Example I gives a substantial yield of amyl 2-methyl-3-sulfo1anyl sulfone, a white solid soluble in ethyl alcohol.

Example VI Phenyl mercaptan is reacted with 3-sulfolene in the presence of sodium hydroxide to produce phenyl 3-sulfolanyl sulfide. When this sulfide is oxidized with hydrogen peroxide a good yield of phenyl 3-sulfolanyl sulfone is obtained.

In the same way the addition products of 3- sulfolene with p-chlorophenyl mercaptan and beta-naphthiol give, on oxidation with hydrogen peroxide, p-chlorophenyl 3-sulfolanyl sulfone and beta-naphthyl 3-sulfolanyl sulfone, respectively.

' By following the procedure described in the foregoing example, neopentyl 3-chloro-4-sulfolanyl sulfone may be produced from neopentyl 3-chloro-4-sulfolanyl sulfide; octyl 3-sulfolanyl sulfone may be produced from octyl 3-sulfolanyl sulfide; cetyl 3-hydroxy1-4-sulfolanyl sulfone from cetyl 3-hydroxy-4-sulfolanyl sulfide; 3,3,5- trimethylcyclohexyl 2 methyl-5-sulfolanyl sulfone may be obtained from 3,3,5-trimethylcyclohexyl 2-methyl-5-sulfolanyl sulfide; benzyl 3-sulfolanyl sulfone from benzyl 3-sulf0lanyl sulfide; tetrahydrofurfuryl 3,4-dichlOromethyl-Z-sulfolanyl sulfone from tetrahydrofurfury-l 3,4-dichloromethyl-Z-sulfolanyl sulfide; phenyl 3-nitro-4- sulfolanyl sulfone from phenyl 3-m'tro-4-sulfolanyl sulfide; 2-chloroallyl 3-suliolanyl sulfone ,from 2-chloroallyl 3-sulfolanyl sulfide; and 3- fide radicals attached to nuclear carbon atoms of the sulfolanyl radical as in 'dimethyl 3,4-sulof April 15, 1947.

8 and the like, the oxidation may be controlled by using reduced amounts of oxidizing agent so as to produce a sulfide substituted monosulfone, 3-

thiomethoxyl-sulfolanyl methyl sulfone:

o OH3-SHOOHH-OH:

as the predominant product or both sulfide sulfur atoms may be oxidized to obtain dimethyl 3,4- sulfoleny-l disulfone. This is also the case in the oxidation of bis-3-(n-propyl 4-sulfolanyl sulfide) ether CHa-OHrOHg-SHO-OHO-HCGH-S-OHz-GHrCH HzI J Hz H2 5H2 I which yields the corresponding monoand disulfones or mixtures thereof, depending upon the concentration of oxidizing agent maintained in the reaction mixture and the total amount of such agent used.

Example VII Equal molecular amounts of 3-iodosulfolane and the potassium salt of 3-methylbutanesulfinic acid are reacted in water made slightly alkaline with potassium hydroxide for an hour at about C. The resulting amyl-sulfolanyl sulfone is separated from the potassium iodide solution formed in the reaction and is purified by recrystallization from alcohol and is obtained as a White product melting at about 102C.

By the method of Example VII stearyl 3-sulfolanyl sulfone may be produced by using'stearyl and 3-sulfolanesulfinic acid potassium salt, and vinyl 3-su1 folanyl sulfone may be obtained by using vinyl iodide in place of the stearyl iodide, and preferably carrying out the reaction in the presence of sufficient of a polymerization inhibitor such as hydroquinone, p-t-butyl-catechol, etc. to prevent substantial losses through polymerization, In the same way, using a polymerization inhibitor 3-allyl-4-iodosulfolane is reacted with ethanesulfinic acid potassium salt to obtain ethyl 3-allyl-4-sulfolanyl sulfone and propargyl iodide is reacted with the potassium salt of 3-amino-4- sulfolanesulfinic acid. The sulfolanyl sulfones of the invention produced in the foregoing or other suitable Ways may be further reacted to produce other derivatives having valuable properties. Thus, those having hydroxyl or carboxylic acid groups in the molecule may be esterified, for example as described and claimed in copending application, Serial No. 495,376, filed July 19, 1943, or those containing a hydroxy group may be converted to ethers by the process of copending application, Serial No. 446,130, filed June 6, 1942, now Patent 2,419,082 The new products may be halogenated and/0r alkylated. They can also be used as intermediates in the production of other types of compounds. It will thus be seen that the invention offers many advantages and provides for the production of a wide variety of novel; sulfolanyl sulfones which have many practical industrial applications. The new compounds are particularly useful in the natural and synthetic resin and lacquer industries; they are useful ingredients of insecticidal, parasiticidal and fungicidal'compositions. When sulfonated, they may serve as wetting and emulsifying agents or the like. It will therefore be seen that the invention is capable-of many variations and is not restricted to the compounds and methods described byway of illustration 3 nor by any theory suggested in explanation of the improved results which are achieved.

We claim as our invention:

1. Amyl S-sulio'lanyl su'lione of the structural formula cfinwsor-onp-onz 2. An aryl 3-sulfo1anyl sulfone of the structural formula RS02CH20H2 Where R is a monovalent aliphatic hydrocarbon radical which is directly attached to the 3-sulfonyl radical by a saturated carbon atom.

5. A sulfolanyl sulfone having directly attached to a nuclear carbon atom of the solfolanyl radical, a single sulfonyl radical to which a monovalent aliphatic hydrocarbon radical of not more than 20 carbon atoms is also directly attached and having the structural formula where one of the His is a radical of the structure 0 H r-S- wherein R1 is monovalent aliphatic hydrocarbon radical of not more than 20 carbon atoms and.

the remaining Rs each represent a hydrogen atom.

6. A sulfolanyl sulfone having directly attached to a nuclear carbon atom of the sulfoanyl radical, a sulfonyl radical which is also directly linked to a carbon atom of an aromatic group and having the structural formula where one of the Rs is a radical of the structure.

o H vals wherein R1 is an aromatic hydrocarbon radical and the remaining Rs each represent a hydrogen atom.

'7. A 3-sulfolany1 sulfone having directly attached to a nuclear carbon atom of the sulfolanyl radical, a sulfonyl radical which isalso directly attached to a hydrocarbon radical and having the structural formula where R is a monovalent hydrocarbon radical of.

not more than 20 carbon atoms.

. 8. The process of producing a polysulfone whereby a sulfone sulfide compound of the structural formula wherein at least one of the Rs is a radical of the structure R1S, where R1 is a monovalent hydrocarbon radical of not more than 20 carbon atoms, and wherein the remaining Rs each represents a member of the group consisting of the hydrogen atom and the lower alkyl radicals, is treated with an oxidizing agent at a temperature between 40 C. and 150 (3., said treatment converting each radical of the structure Ri-S- to a radical of the structure 9. The process of claim 8 wherein R1 is an alkyl radical of not more than 20 carbon atoms and wherein the compound of structural formula i R R-co 11 R;C\ 5 R R s \R o o is treated with a stoichiometrical excess of potassium permanganate at a temperature between 50 C. and C. for from 20 to minutes. 10. A polysulione of thestructural formula 11 12 5 wherein at least one of the Rs is a radical of the v REFERENCES CITED structure 7 1 I O The following references are of record in the R g file of this patent:

5 UNITED STATES PATENTS Number Name Date in which R1 is a monovalent hydrocarbon radical of not more than 20 carbon atoms, and wherein the remaining Rs each represents a member of In OTHER REFERENCES the group consisting of the hydrogen atom and the lower alkyl radicals Backer. Rec. Trav. Ch1m., 56, 181 (1937).

RUPERT C. MORRIS. EDWARD C. SHOKAL.

2,291,798 Delfs Aug. 4:, 1942. 

